Photosensitive resin composition

Abstract

To provide a photosensitive resin composition which has excellent resolution and can suppress the occurrence of connection failure in a via hole having a smaller diameter and can form an insulation layer having more excellent copper plating peel strength.SOLUTION: There is provided a photosensitive resin composition which is a resin composition comprising (A) an epoxy resin, (B) an acid-modified epoxy (meth)acrylate resin, (C) a photopolymerization initiator and (D) an inorganic filler, wherein the component (D) includes (D1) an inorganic filler having an average particle diameter of 20 to 90 nm and (D2) an inorganic filler having an average particle diameter of 100 to 500 nm and the component (D1) includes an inorganic filler surface-treated with an amino-based silane coupling agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition. Furthermore, it relates to a photosensitive film with a support, a printed circuit board, and a semiconductor device obtained using the photosensitive resin composition. [Background technology]

[0002] In printed circuit boards, a solder resist is sometimes provided as a permanent protective film to prevent solder from adhering to areas where solder is not needed and to prevent corrosion of the circuit board. A photosensitive resin composition, such as that described in Patent Document 1, is commonly used as the solder resist. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-115672 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In recent years, with the further miniaturization and increased density of wiring in printed circuit boards, it has become necessary to form smaller via holes and finer wiring patterns with smaller metal areas, requiring high resolution. However, when resolution is further improved, new problems have been discovered, such as the inorganic filler material easily falling off the via hole walls and dropping to the bottom of the via holes in smaller diameter via holes, resulting in reduced connection reliability, and the surface roughness of the insulating layer increasing and the copper plating peel strength decreasing because not only the uncured parts but also the cured parts (the parts that become the insulating layer) are more easily treated with the chemical solution.

[0005] The object of the present invention is to provide a photosensitive resin composition that has excellent resolution, can suppress the occurrence of connection failures in reduced-diameter via holes, and can form an insulating layer with superior copper plating peel strength. [Means for solving the problem]

[0006] As a result of diligent research by the present inventors, we have found that by using a photosensitive resin composition comprising (A) epoxy resin, (B) acid-modified epoxy (meth)acrylate resin, (C) photopolymerization initiator, and (D) inorganic filler, wherein (D) inorganic filler comprises (D1) inorganic filler with an average particle size of 20 nm to 90 nm and (D2) inorganic filler with an average particle size of 100 nm to 500 nm, and component (D1) is an inorganic filler surface-treated with an amino-based silane coupling agent, it is possible to achieve excellent resolution, suppress the occurrence of connection failures in reduced-diameter via holes, and form an insulating layer with superior copper plating peel strength, thus completing the present invention.

[0007] In other words, the present invention includes the following: [1] A resin composition comprising (A) epoxy resin, (B) acid-modified epoxy (meth)acrylate resin, (C) photopolymerization initiator, and (D) inorganic filler, Component (D) includes (D1) an inorganic filler with an average particle size of 20 nm to 90 nm, and (D2) an inorganic filler with an average particle size of 100 nm to 500 nm. A photosensitive resin composition comprising (D1) an inorganic filler surface-treated with an amino-based silane coupling agent. [2] The photosensitive resin composition according to [1] above, wherein the content of component (D1) is 5% to 30% by mass, when the nonvolatile components in the resin composition are taken as 100% by mass. [3] The photosensitive resin composition according to [1] or [2] above, wherein the content of component (D2) is 20% by mass or more when the nonvolatile components in the resin composition are taken as 100% by mass. [4] A photosensitive resin composition according to any one of [1] to [3] above, wherein component (D2) comprises an inorganic filler surface-treated with an amino-based silane coupling agent. [5] A photosensitive resin composition according to any one of [1] to [4] above, wherein the mass ratio of component (D2) to component (D1) (component (D2) / component (D1)) is 0.5 to 20. [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein the content of component (D) is 40% by mass or more when the nonvolatile components in the photosensitive resin composition are taken as 100% by mass. [7] A photosensitive resin composition according to any one of [1] to [6] above, wherein component (A) comprises an epoxy resin having a naphthalene skeleton. [8] A photosensitive resin composition according to any one of [1] to [7] above, wherein component (B) comprises an acid-modified epoxy (meth)acrylate resin having a naphthalene skeleton. [9] A photosensitive resin composition according to any of [1] to [8] above, wherein the acid value of component (B) is 1 mg KOH / g or more.

[10] The photosensitive resin composition according to any of [1] to [9] above, wherein the weight-average molecular weight of component (B) is 1,000 to 20,000.

[11] A photosensitive resin composition according to any of [1] to

[10] above, wherein the mass ratio of component (B) to component (A) (component (B) / component (A)) is 1 to 3.

[12] A photosensitive resin composition according to any one of [1] to

[11] above, wherein component (C) contains a photopolymerization initiator selected from α-aminoketone-based photopolymerization initiators and phosphine oxide-based photopolymerization initiators.

[13] The photosensitive resin composition according to

[12] above, wherein component (C) comprises an α-aminoketone-based photopolymerization initiator having a fluorene skeleton.

[14] (E) A photosensitive resin composition according to any one of [1] to

[13] above, further comprising a photosensitizer.

[15] The photosensitive resin composition according to

[14] above, wherein component (E) comprises a photosensitizer selected from thioxanthones and benzophenones.

[16] A photosensitive resin composition according to any of [1] to

[15] above, for use in forming solder resist.

[17] A photosensitive film with a support, comprising a support and a photosensitive resin composition layer formed of any of the photosensitive resin compositions described in [1] to

[16] above, provided on the support.

[18] The photosensitive film according to

[17] above, wherein the thickness of the photosensitive resin composition layer is in the range of 10 μm to 100 μm.

[19] A printed circuit board comprising an insulating layer formed from a cured product of any of the photosensitive resin compositions described in [1] to

[16] above.

[20] A semiconductor device including the printed circuit board described in

[19] above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a photosensitive resin composition that has excellent resolution, can suppress the occurrence of connection failures in reduced-diameter via holes, and can form an insulating layer with superior copper plating peel strength. [Modes for carrying out the invention]

[0009] The present invention will be described in detail below with reference to its preferred embodiments. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with modifications as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0010] <Photosensitive resin composition> The photosensitive resin composition of the present invention comprises (A) an epoxy resin, (B) an acid-modified epoxy (meth)acrylate resin, (C) a photopolymerization initiator, and (D) an inorganic filler, wherein (D) the inorganic filler comprises (D1) an inorganic filler with an average particle size of 20 nm to 90 nm and (D2) an inorganic filler with an average particle size of 100 nm to 500 nm, and component (D1) comprises an inorganic filler surface-treated with an amino-based silane coupling agent. Such a photosensitive resin composition has excellent resolution, can suppress the occurrence of connection failures in reduced-diameter via holes, and enables the formation of an insulating layer with superior copper plating peel strength.

[0011] The photosensitive resin composition of the present invention may further contain any optional components in addition to (A) epoxy resin, (B) acid-modified epoxy (meth)acrylate resin, (C) photopolymerization initiator, and (D) inorganic filler. Examples of optional components include (E) photosensitizer, (F) reaction diluent, (G) organic solvent, and (H) other additives. Each component contained in the resin composition will be described in detail below.

[0012] <(A) Epoxy resin> The photosensitive resin composition of the present invention contains (A) an epoxy resin. (A) The epoxy resin is a curable resin having epoxy groups.

[0013] (A) Examples of epoxy resins include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiroring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthaleimidine type epoxy resin, and the like. (A) Epoxy resin may be used alone or in combination of two or more types.

[0014] The photosensitive resin composition of the present invention preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) epoxy resin. The proportion of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of (A) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0015] (A) Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The photosensitive resin composition of the present invention may contain only liquid epoxy resin, or only solid epoxy resin, or both liquid epoxy resin and solid epoxy resin, but it is particularly preferable to contain only solid epoxy resin or both liquid epoxy resin and solid epoxy resin.

[0016] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0017] Preferred liquid epoxy resins include glycirol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, phenol novolac-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cyclic aliphatic glycidyl ethers, and epoxy resins having a butadiene structure.

[0018] Specific examples of liquid epoxy resins include "EX-992L" from Nagase ChemteX, "YX7400" from Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) from DIC Corporation; "828US", "jER828EL", "828EL", "825", and "Epicote 828EL" (bisphenol A-type epoxy resin) from Mitsubishi Chemical Corporation; and "jER807" and "1750" from Mitsubishi Chemical Corporation. Bisphenol F type epoxy resin; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycyrol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "EX-991L" (epoxy resin containing alkylene oxy skeleton and butadiene skeleton) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation Examples include "PB-3600" from Daicel Corporation, "JP-100" and "JP-200" from Nippon Soda Co., Ltd. (epoxy resins with a butadiene structure); "ZX1658" and "ZX1658GS" from Nippon Steel Chemical & Material Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resins); "EG-280" from Osaka Gas Chemical Co., Ltd. (fluorene structure-containing epoxy resin); and "EX-201" from Nagase ChemteX Corporation (cyclic aliphatic glycidyl ether).

[0019] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

[0020] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolac-type epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, phenol aralkyl-type epoxy resin, tetraphenylethane-type epoxy resin, and phenolphthaleimidine-type epoxy resin.

[0021] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resins); and DIC's "EXA-7311". "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V", "ESN4 100V (naphthalene-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "Y Examples include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) from Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) from Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) from Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) from Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalein type epoxy resin) from Nippon Kayaku Co., Ltd.These may be used individually or in combination of two or more types.

[0022] (A) When using a combination of solid epoxy resin and liquid epoxy resin as the epoxy resin, the mass ratio of the solid epoxy resin to the liquid epoxy resin is preferably 10:1 to 1:50, more preferably 5:1 to 1:20, and particularly preferably 2:1 to 1:10.

[0023] (A) The epoxy resin preferably includes an epoxy resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton, and is particularly preferably an epoxy resin having a naphthalene skeleton.

[0024] (A) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0025] (A) The weight-average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight-average molecular weight of the resin can be measured as a polystyrene equivalent by gel permeation chromatography (GPC).

[0026] (A) The epoxy resin content is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more, when the nonvolatile components of the photosensitive resin composition are considered to be 100% by mass. The upper limit is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0027] <(B) Acid-modified epoxy (meth)acrylate resin> The photosensitive resin composition of the present invention contains (B) an acid-modified epoxy (meth)acrylate resin.

[0028] (B) Since the acid-modified epoxy (meth)acrylate resin has acidic groups such as carboxyl groups, the photosensitive resin composition of the present invention may, in one embodiment, be soluble in an alkaline developer (for example, a 1% by mass aqueous solution of sodium carbonate). (B) The number of acidic groups (for example, carboxyl groups) per molecule of the acid-modified epoxy (meth)acrylate resin may be one or two or more.

[0029] (B) The acid-modified epoxy (meth)acrylate resin has (meth)acryloyl groups (acryloyl groups or methacryloyl groups), and in one embodiment, photoradical polymerization may be possible. (B) The number of (meth)acryloyl groups per molecule of the acid-modified epoxy (meth)acrylate resin may be one or two or more.

[0030] (B) The acid-modified epoxy (meth)acrylate resin is preferably a resin that has both (meth)acryloyl groups and carboxyl groups, and that enables photoradical polymerization and alkali development.

[0031] (B) Acid-modified epoxy (meth)acrylate resins can be produced by acid-modifying epoxy (meth)acrylate resins using known methods. For example, epoxy (meth)acrylate resins can be produced by reacting epoxy resin with acrylic acid or methacrylic acid.

[0032] The epoxy resin used for the production of epoxy (meth)acrylate resins is not particularly limited as long as it is a compound having an epoxy group in its molecule. Examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, and modified bisphenol F type epoxy resin obtained by reacting bisphenol F type epoxy resin with epichlorohydrin to modify it into a trifunctional or more complex resin; biphenol type epoxy resins such as biphenol type epoxy resin and tetramethylbiphenol type epoxy resin; novolac type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, and alkylphenol novolac type epoxy resin; fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, naphthol type epoxy resin, and naphthol aralkyl type epoxy resin. Epoxy resins containing a naphthalene skeleton, such as lipids, binaphthol-type epoxy resins, naphthylene ether-type epoxy resins, naphthol novolac-type epoxy resins, and naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes (naphthalene skeleton-containing epoxy resins); bixylenol-type epoxy resins; dicyclopentadiene-type epoxy resins; trisphenol-type epoxy resins; tert-butyl-catechol-type epoxy resins; anthracene-type epoxy resins; and glycidylamine-type epoxy resins. Examples include epoxy resins; glycidyl ester type epoxy resins; biphenyl type epoxy resins; linear aliphatic epoxy resins; epoxy resins having a butadiene structure; alicyclic epoxy resins; heterocyclic epoxy resins; spiroring-containing epoxy resins; cyclohexanedimethanol type epoxy resins; trimethylol type epoxy resins; tetraphenylethane type epoxy resins; glycidyl group-containing acrylic resins such as polyglycidyl (meth)acrylate and copolymers of glycidyl methacrylate and acrylic acid esters; fluorene type epoxy resins; halogenated epoxy resins, etc.

[0033] For the production of epoxy (meth)acrylate resins, epoxy resins containing an aromatic skeleton are preferred from the viewpoint of reducing the mean linear thermal expansion coefficient. Here, the aromatic skeleton is a concept that also includes polycyclic aromatics and aromatic heterocyclics. Among these, any of the following are preferred: cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and naphthol aralkyl type epoxy resin.

[0034] (B) In one embodiment, the acid-modified epoxy (meth)acrylate resin preferably includes an acid-modified epoxy (meth)acrylate resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton, and is particularly preferably an acid-modified epoxy (meth)acrylate resin having a naphthalene skeleton.

[0035] (B) In one embodiment, the acid-modified epoxy (meth)acrylate resin preferably includes a resin selected from an acid-modified epoxy (meth)acrylate resin in which the hydroxyl groups of the epoxy (meth)acrylate resin are esterified (hereinafter referred to as "ester-type acid-modified epoxy (meth)acrylate resin") and an acid-modified epoxy (meth)acrylate resin in which the hydroxyl groups of the epoxy (meth)acrylate resin are urethane-modified (hereinafter referred to as "urethane-type acid-modified epoxy (meth)acrylate resin"), and it is particularly preferable that it includes an ester-type acid-modified epoxy (meth)acrylate resin.

[0036] (Ester-type acid-modified epoxy (meth)acrylate resin) Ester-type acid-modified epoxy (meth)acrylate resins can be produced, for example, by reacting epoxy (meth)acrylate resin with a polycarboxylic acid anhydride. Ester-type acid-modified epoxy (meth)acrylate resins may be used individually or in combination of two or more types.

[0037] Examples of polycarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. These may be used individually or in combination of two or more. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred, with tetrahydrophthalic anhydride being more preferred.

[0038] The ester-type acid-modified epoxy (meth)acrylate resin preferably includes a resin selected from cresol novolac skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin, bisphenol A skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin, bisphenol F skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin, biphenyl skeleton-containing acid ester-type modified epoxy (meth)acrylate resin, and naphthol aralkyl skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin.

[0039] Ester-type acid-modified epoxy (meth)acrylate resins can be synthesized by known methods, but commercially available products may also be used. Specific examples of commercially available products include Nippon Kayaku Co., Ltd.'s "CCR-1373H" (cresol novolac skeleton-containing acid-modified epoxy acrylate resin), "ZCR-8001H" (biphenyl skeleton-containing acid-modified epoxy acrylate resin), "ZCR-1569H" (biphenyl skeleton-containing acid-modified epoxy acrylate resin), "CCR-1171H" (cresol novolac skeleton-containing acid-modified epoxy acrylate resin), and "ZCR-1797H" (biphenyl skeleton-containing acid-modified epoxy acrylate resin). Examples of acrylate resins include "ZAR-2000" (bisphenol A skeleton-containing acid-modified epoxy acrylate resin), "ZFR-1491H", and "ZFR-1533H" (bisphenol F skeleton-containing acid-modified epoxy acrylate resins) from Nippon Kayaku Co., Ltd., "PR-300CP" (cresol novolac type acid-modified epoxy acrylate resin) from Showa Denko Corporation, and "CCR-1179" (cresol novolac skeleton-containing epoxy acrylate resin) from Nippon Kayaku Co., Ltd.

[0040] (Urethane-type acid-modified epoxy (meth)acrylate resin) Urethane-type acid-modified epoxy (meth)acrylate resins can be produced, for example, by reacting epoxy (meth)acrylate resin with a diisocyanate compound and a carboxyl group-containing diol compound. Urethane-type acid-modified epoxy (meth)acrylate resins may be used individually or in combination of two or more types.

[0041] Examples of diisocyanate compounds include aromatic diisocyanate compounds such as phenylenediisocyanate, tolylenediisocyanate, xylylenediisocyanate, tetramethylxylylenediisocyanate, diphenyldiisocyanate, and naphthalenediisocyanate; and aliphatic diisocyanate compounds such as hexamethylenediisocyanate, dicyclohexylmethanediisocyanate, isophoronediisocyanate, allylenesulfone etherdiisocyanate, allylcyanidediisocyanate, N-acyldiisocyanate, trimethylhexamethylenediisocyanate, and 1,3-bis(isocyanatemethyl)cyclohexane.

[0042] Examples of carboxyl group-containing diol compounds include dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolnonanoic acid.

[0043] The urethane-type acid-modified epoxy (meth)acrylate resin preferably contains a resin selected from cresol novolac skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin, bisphenol A skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin, bisphenol F skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin, biphenyl skeleton-containing acid urethane-type modified epoxy (meth)acrylate resin, and naphthol aralkyl skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin.

[0044] Urethane-type acid-modified epoxy (meth)acrylate resins can be synthesized by known synthesis methods, but commercially available products may also be used. Examples of known synthesis methods include the method described in Japanese Patent Publication No. 2016-199719. Specific examples of commercially available products include "UXE-3024," "UXE-3011," "UXE-3012," and "UXE-3024" manufactured by Nippon Kayaku Co., Ltd.

[0045] (B) The acid value of the acid-modified epoxy (meth)acrylate resin is preferably 0.1 mg KOH / g or more, more preferably 0.5 mg KOH / g or more, even more preferably 1 mg KOH / g or more, 10 mg KOH / g or more, even more preferably 20 mg KOH / g or more, 30 mg KOH / g or more, and particularly preferably 40 mg KOH / g or more, 50 mg KOH / g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition. (B) The upper limit of the acid value of the acid-modified epoxy (meth)acrylate resin is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less, from the viewpoint of improving insulation reliability.

[0046] (B) The weight-average molecular weight of the acid-modified epoxy (meth)acrylate resin is preferably 20,000 or less, more preferably 17,000 or less, and even more preferably 15,000 or less. (B) The lower limit of the weight-average molecular weight of the acid-modified epoxy (meth)acrylate resin is preferably 1,000 or more, more preferably 1,500 or more. The weight-average molecular weight is the weight-average molecular weight on a polystyrene basis measured by gel permeation chromatography (GPC).

[0047] (B) The content of the acid-modified epoxy (meth)acrylate resin is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more, when the nonvolatile components of the photosensitive resin composition are considered to be 100% by mass, from the viewpoint of improving alkali developability. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less, from the viewpoint of improving heat resistance.

[0048] The mass ratio of (B) acid-modified epoxy (meth)acrylate resin to (A) epoxy resin (component (B) / component (A)) is preferably 0.1 or higher, more preferably 0.5 or higher, and even more preferably 1 or higher. The upper limit is preferably 30 or lower, more preferably 10 or lower, and even more preferably 3 or lower.

[0049] <(C) Photopolymerization initiator> The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator.

[0050] (C) Examples of photopolymerization initiators include α-aminoketone-based photopolymerization initiators, phosphine oxide-based photopolymerization initiators, α-hydroxyketone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, benzoin-based photopolymerization initiators, and benzyl ketal-based photopolymerization initiators.

[0051] Examples of phosphine oxide-based photopolymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphine] (Polymeric TPO-L).

[0052] Examples of α-hydroxyketone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one.

[0053] Examples of oxime ester-based photopolymerization initiators include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01) and [1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethylideneamino]acetate (OXE02).

[0054] Examples of benzoin-based photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of benzyl ketal-based photopolymerization initiators include 2,2-dimethoxy-2-phenylacetophenone.

[0055] As α-aminoketone photopolymerization initiators, for example, α-aminoketone photopolymerization initiators without a fluorene skeleton such as 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and 2-(dimethylamino)-2-(4-methylphenylmethyl)-1-(4-morpholinophenyl)butan-1-one may be used, but it is preferable to use α-aminoketone photopolymerization initiators that have a fluorene skeleton.

[0056] (C) In one embodiment, the photoinitiator preferably includes a photoinitiator selected from an α-amino ketone-based photoinitiator and a phosphine oxide-based photoinitiator, more preferably includes an α-amino ketone-based photoinitiator, and particularly preferably includes an α-amino ketone-based photoinitiator having a fluorene skeleton.

[0057] In one embodiment, the α-amino ketone-based photoinitiator having a fluorene skeleton preferably has the formula (1):

[0058] [Chemical formula]

[0059] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each independently represent a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, -SOR, -SO2R, -COR, -OCOR, -COOR, or -CONR2; R each independently represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an aryl group optionally having a substituent, an aralkyl group optionally having a substituent, or a heterocyclic group optionally having a substituent; R 8 , and R 9 each independently represent a hydrogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, or an aralkyl group optionally having a substituent, or R 8 , and R 9 are bonded together to form a non-aromatic carbocyclic ring optionally having a substituent; R a , and R bEach independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R a , and R b They combine and bond to form a non-aromatic carbon ring which may have substituents; R c , and R d Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R c , and R d These elements combine and bond to form a nitrogen-containing heterocycle, which may have substituents. It contains compounds represented by [formula].

[0060] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each independently represents a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, -SOR, -SO2R, -COR, -OCOR, -COOR, or -CONR2; in one embodiment, preferably a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, or -COR; more preferably R 1 , R 3 , R 4 , R 5 , R 6 , and R 7 However, it is a hydrogen atom, and R 2 is a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, or -COR; particularly preferably a hydrogen atom.

[0061] Each R independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted heterocyclic group.

[0062] Alkyl(group) refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, alkyl(groups) having 1 to 14 carbon atoms are preferred, alkyl(groups) having 1 to 10 carbon atoms are more preferred, and alkyl(groups) having 1 to 6 carbon atoms are even more preferred. Examples of alkyl(groups) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, sec-pentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, tert-octyl group, cyclopentyl group, cyclohexyl group, and cyclohexylmethyl group.

[0063] An alkenyl(group) refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl(groups) having 2 to 14 carbon atoms are preferred, alkenyl(groups) having 2 to 10 carbon atoms are more preferred, and alkenyl(groups) having 2 to 6 carbon atoms are even more preferred. Examples of alkenyl groups include vinyl groups, propenyl groups (allyl group, 1-propenyl group, isopropenyl group), butenyl groups (1-butenyl group, clotyl group, methallyl group, isoclotyl group, etc.), pentenyl groups (1-pentenyl group, etc.), hexenyl groups (1-hexenyl group, etc.), heptenyl groups (1-heptenyl group, etc.), octenyl groups (1-octenyl group, etc.), cyclopentenyl groups (2-cyclopentenyl group, etc.), and cyclohexenyl groups (3-cyclohexenyl group, etc.).

[0064] An aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, aryl groups with 6 to 14 carbon atoms are preferred, and aryl groups with 6 to 10 carbon atoms are particularly preferred. Examples of aryl groups include phenyl groups, 1-naphthyl groups, and 2-naphthyl groups.

[0065] An aralkyl group refers to an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, aralkyl groups with 7 to 15 carbon atoms are preferred, and aralkyl groups with 7 to 11 carbon atoms are particularly preferred. Examples of aralkyl groups include benzyl group, phenethyl group, hydrocinnamyl group, α-methylbenzyl group, α-cumyl group, 1-naphthylmethyl group, and 2-naphthylmethyl group.

[0066] A heterocyclic group is a monovalent cyclic group consisting of a carbon atom and heteroatoms such as oxygen, nitrogen, and sulfur atoms as ring constituent atoms, with one hydrogen atom removed. Heterocyclic groups with 4 to 15 members are preferred, and heterocyclic groups with 5 to 10 members are more preferred. Heterocyclic groups can be aromatic heterocyclic groups that follow Hückel's rule, where the number of electrons in the π-electron system on the ring is 4p+2 (where p is a natural number), and non-aromatic heterocyclic groups other than aromatic heterocyclic groups where the entire ring is not aromatic, but in one embodiment, non-aromatic heterocyclic groups are preferred. Examples of heterocyclic groups include pyrrolidinyl groups (such as N-pyrrolidinyl groups), pyrazolidinyl groups (such as N-pyrazolidinyl groups), imidazolidinyl groups (such as N-imidazolidinyl groups), piperidinyl groups (such as N-piperidinyl groups), morpholinyl groups (such as N-morpholinyl groups), and thiomorpholinyl groups (such as N-thiomorpholinyl groups).

[0067] The "substituents" of alkyl and alkenyl groups are not particularly limited, but examples include halogen atoms, nitro groups, amino groups, hydroxyl groups, aryl groups, alkyl-aryl groups (aryl groups substituted with one or more alkyl groups), alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, aralkyl-oxy groups, alkyl-carbonyl groups, alkenyl-carbonyl groups, aryl-carbonyl groups, aralkyl-carbonyl groups, alkyl-oxy-carbonyl groups, alkenyl-oxy-carbonyl groups, aryl-oxy-carbonyl groups, aralkyl-oxy-carbonyl groups, alkyl-carbonyl-oxy groups, alkenyl-carbonyl-oxy groups, aryl-carbonyl-oxy groups, aralkyl-carbonyl-oxy groups, mono or di(alkyl)amino groups, mono or di(alkenyl)amino groups, heterocyclic groups, etc.

[0068] The "substituents" of aryl groups, aralkyl groups, and heterocyclic groups are not particularly limited, but examples include halogen atoms, nitro groups, amino groups, hydroxyl groups, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl-aryl groups, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, aralkyl-oxy groups, alkyl-carbonyl groups, alkenyl-carbonyl groups, aryl-carbonyl groups, aralkyl-carbonyl groups, alkyl-oxy-carbonyl groups, alkenyl-oxy-carbonyl groups, aryl-oxy-carbonyl groups, aralkyl-oxy-carbonyl groups, alkyl-carbonyl-oxy groups, alkenyl-carbonyl-oxy groups, aryl-carbonyl-oxy groups, aralkyl-carbonyl-oxy groups, mono or di(alkyl)amino groups, mono or di(alkenyl)amino groups, heterocyclic groups, etc.

[0069] In one embodiment, R is preferably independently an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group; more preferably (1) an alkyl group which may be substituted with a group selected from a halogen atom, a nitro group, a hydroxyl group, an aryl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, a mono- or di(alkyl)amino group, and a heterocyclic group; (2) an aryl group which may be substituted with a group selected from a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, a mono- or di(alkyl)amino group, and a heterocyclic group; or ( 3) A heterocyclic group which may be substituted with a group selected from halogen atoms, nitro groups, hydroxyl groups, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl-aryl groups, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, aralkyl-oxy groups, mono or di(alkyl)amino groups, and heterocyclic groups; particularly preferably, (1) an alkyl group which may be substituted with a group selected from nitro groups, hydroxyl groups, alkyl-oxy groups, mono or di(alkyl)amino groups, and heterocyclic groups; (2) an aryl group which may be substituted with a group selected from nitro groups, alkyl groups, alkyl-oxy groups, mono or di(alkyl)amino groups, and heterocyclic groups; or (3) a heterocyclic group which may be substituted with a group selected from nitro groups, alkyl groups, alkyl-oxy groups, mono or di(alkyl)amino groups, and heterocyclic groups.

[0070] R 8 , and R 9 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R 8 , and R 9 These combine and bond to form a non-aromatic carbon ring, which may have substituents.

[0071] A non-aromatic carbocyclic ring refers to a carbocyclic ring that does not possess aromaticity throughout the entire ring. A non-aromatic carbocyclic ring consists only of carbon atoms. A non-aromatic carbocyclic ring can be a saturated carbocyclic ring consisting only of single bonds, or an unsaturated carbocyclic ring having at least one of two or three bonds. A non-aromatic carbocyclic ring also includes a fused ring that has some aromaticity, formed when a non-aromatic ring condenses with an aromatic ring. Non-aromatic carbocyclic rings with 4 to 20 carbon atoms are preferred, and non-aromatic carbocyclic rings with 5 to 12 carbon atoms are more preferred. Suitable examples of non-aromatic carbocyclic rings include, for example, monocyclic saturated carbocyclic rings such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane rings; bicyclic saturated carbocyclic rings such as bicyclo[2.2.1]heptane (norbornane), bicyclo[4.4.0]decane (decalin), bicyclo[5.3.0]decane, bicyclo[4.3.0]nonane (hydrindan), bicyclo[3.2.1]octane, bicyclo[5.4.0]undecane, bicyclo[3.3.0]octane, and bicyclo[3.3.1]nonane rings; and tricyclo[5.2.1.0 2,6 ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 ] Decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 ]Saturated tricyclic carbocyclic rings such as undecane rings; tetracyclo[6.2.1.1 3,6 .0 2,7 ]Saturated tetracyclic carbocyclic rings such as dodecane rings; pentacyclo[9.2.1.1 4,7 .0 2,1 .0 3,8 ]Pentadecane ring, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 Examples include pentadecane rings (tetrahydrotricyclopentadiene rings) and other pentagonal saturated carbon rings.

[0072] Examples of "substituents" for non-aromatic carbon rings include those similar to the "substituents" for aryl groups, aralkyl groups, and heterocyclic groups exemplified above.

[0073] R 8 , and R 9 In one embodiment, each is preferably independently a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted alkenyl group, or R 8 , and R 9 These groups bond together to form a monocyclic saturated carbon ring which may have substituents; more preferably, (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, and a mono or di(alkyl)amino group, or (3) an alkenyl group which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, and a mono or di(alkyl)amino group, or R 8 , and R 9 These groups bond together to form a cyclopentane ring or a cyclohexane ring; more preferably, a hydrogen atom, an alkyl group, or an alkenyl group; even more preferably, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; particularly preferably, a propyl group, a butyl group, or a pentyl group.

[0074] R a , and R b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R a , and R b These combine and bond to form a non-aromatic carbon ring, which may have substituents.

[0075] R a , and R b In one embodiment, each is preferably independently an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R a , and R bThese groups bond together to form a monocyclic saturated carbon ring which may have substituents; more preferably, (1) an alkyl group which may be substituted with a group selected from a halogen atom, alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, aralkyl-oxy group, and mono or di(alkyl)amino group, (2) an alkenyl group which may be substituted with a group selected from a halogen atom, alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, aralkyl-oxy group, and mono or di(alkyl)amino group, or (3) an aralkyl group which may be substituted with a group selected from a halogen atom, alkyl group, alkenyl group, alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, aralkyl-oxy group, and mono or di(alkyl)amino group, or R a , and R b These groups bond together to form a cyclopentane ring or a cyclohexane ring; more preferably, (1) an alkyl group, (2) an alkenyl group, or (3) an aralkyl group which may be substituted with an alkyl group; even more preferably, an alkyl group having 1 to 6 carbon atoms; particularly preferably, a methyl group or an ethyl group.

[0076] R c , and R d Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R c , and R d These elements combine and bond to form a nitrogen-containing heterocycle, which may have substituents.

[0077] A nitrogen-containing heterocycle refers to a heterocycle in which at least both carbon atoms and nitrogen atoms are ring constituent atoms, and which may also have heteroatoms other than nitrogen atoms, such as oxygen atoms and sulfur atoms, as ring constituent atoms. The nitrogen-containing heterocycle may be a nitrogen-containing aromatic heterocycle that follows Hückel's rule, in which the number of electrons in the π-electron system on the ring is 4p+2 (where p is a natural number), or it may be a nitrogen-containing non-aromatic heterocycle in which the entire ring is not aromatic, but in one embodiment, a nitrogen-containing non-aromatic heterocycle is preferred. The nitrogen-containing heterocycle may be a monocyclic, bicyclic, or tricyclic nitrogen-containing heterocycle, but in one embodiment, a monocyclic nitrogen-containing heterocycle is preferred. In one embodiment, the nitrogen-containing heterocycle is preferably 3 to 14 members, more preferably 4 to 10 members, and even more preferably 5 or 6 members. Examples of nitrogen-containing heterocycles include pyrrolidine rings, imidazolidine rings, pyrazolidine rings, oxazolidine rings, piperidine rings, morpholine rings, and thiomorpholine rings.

[0078] Examples of "substituents" for nitrogen-containing heterocyclic groups include those similar to the "substituents" for aryl groups, aralkyl groups, and heterocyclic groups exemplified above.

[0079] R c , and R d In one embodiment, each independently preferably represents an alkyl group which may have a substituent, or R c , and R d These combine and bond to form a nitrogen-containing non-aromatic heterocycle which may have substituents; more preferably, it represents an alkyl group having 1 to 6 carbon atoms, or R c , and R d These combine and bond to form a 5 or 6-membered nitrogen-containing non-aromatic heterocycle; more preferably, R c , and R d These combine and bond to form a 5 or 6-membered nitrogen-containing non-aromatic heterocycle; particularly preferably, R c , and R d These molecules combine and bond to form a morpholine ring.

[0080] In one embodiment, the α-aminoketone-based photopolymerization initiator having a fluorene skeleton is particularly preferably of formulas (2-1) to (2-7):

[0081] [ka]

[0082] [Each symbol is defined as described above.] The compound contains any of the following, and is particularly preferably the compound represented by formula (2-1).

[0083] Specific examples of α-aminoketone-based photopolymerization initiators having a fluorene skeleton are not limited to those specified in formulas (3-1) to (3-116):

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] Examples of compounds represented by [the formula shown] are given.

[0091] α-aminoketone photopolymerization initiators having a fluorene skeleton can be easily synthesized using known synthesis methods or similar methods, but commercially available products may also be used. An example of a commercially available α-aminoketone photopolymerization initiator having a fluorene skeleton is TRONLY's "TR-NPI-20400" (the compound represented by formula (3-41), "2-methyl-1-(9,9-dibutylfluoren-2-yl)-2-morpholinopropan-1-one").

[0092] (C) The upper limit of the molecular weight of the photopolymerization initiator is not particularly limited, but is preferably 4000 or less, more preferably 2000 or less.

[0093] (C) The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, when the nonvolatile components of the photosensitive resin composition are taken as 100% by mass. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less.

[0094] <(D) Inorganic filler> The photosensitive resin composition of the present invention contains (D) an inorganic filler. (D) The inorganic filler is included in the photosensitive resin composition in the form of particles.

[0095] (D) Inorganic compounds are used as the material for the inorganic filler. (D) Examples of materials for the inorganic filler include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.

[0096] (D) The inorganic filler preferably includes an inorganic filler formed from a material selected from silica, alumina, and aluminosilicate, and is particularly preferably an inorganic filler formed from silica. Examples of inorganic fillers formed from silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc., with spherical silica being preferred. (D) The inorganic filler may be used alone or in combination of two or more types in any ratio.

[0097] In the photosensitive resin composition of the present invention, (D) inorganic filler comprises (D1) an inorganic filler having an average particle size of 20 nm to 90 nm, and (D2) an inorganic filler having an average particle size of 100 nm to 500 nm. In one embodiment, the particle size distribution of (D) inorganic filler preferably has at least one peak in the range of 20 nm to 90 nm derived from (D1) the inorganic filler having an average particle size of 20 nm to 90 nm, and at least one peak in the range of 100 nm to 500 nm derived from (D2) the inorganic filler having an average particle size of 100 nm to 500 nm.

[0098] (D1) The inorganic filler having an average particle size of 20 nm to 90 nm is preferably 80 nm or less, more preferably 70 nm or less, and even more preferably 60 nm or less. The lower limit of the average particle size is preferably 30 nm or more, more preferably 35 nm or more, and even more preferably 40 nm or more.

[0099] The average particle size of inorganic fillers can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, a volume-based particle size distribution of the inorganic filler is created using a laser diffraction-scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A sample consisting of 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed using ultrasound for 10 minutes. The sample was measured using a laser diffraction-type particle size distribution analyzer with a light source wavelength of 405 nm (blue and red) and a flow cell method to measure the volume-based particle size distribution of the inorganic filler. The average particle size was then calculated as the median diameter from the obtained particle size distribution. An example of a laser diffraction-type particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0100] (D1) The inorganic filler having an average particle size of 20 nm to 90 nm is not particularly limited, but preferably has a specific surface area of ​​30 m². 2 / g or more, comfortably 35m 2 / g or more, more preferably 40m 2 / g or more, particularly preferably 45m 2 It is 1 / g or more. The upper limit of its specific surface area is not particularly limited, but is preferably 300m². 2 / g or less, more preferably 250m 2 / g or less, more preferably 200m 2 / g or less, particularly preferably 150m 2 It is less than / g.

[0101] The specific surface area of ​​inorganic fillers is obtained by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multi-point method.

[0102] (D1) Inorganic fillers with an average particle size of 20 nm to 90 nm include inorganic fillers that have been surface-treated with an amino-based silane coupling agent.

[0103] Examples of amino silane coupling agents include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. Commercially available products include "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-5783", and "KBM-575" manufactured by Shin-Etsu Chemical Co., Ltd.

[0104] (D1) The inorganic filler having an average particle size of 20 nm to 90 nm may further include an inorganic filler that has been surface-treated with an amino-based silane coupling agent.

[0105] Examples of surface treatment agents other than amino-based silane coupling agents include vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, and acid anhydride-based silane coupling agents.

[0106] Examples of vinyl-based silane coupling agents include vinyltrimethoxysilane and vinyltriethoxysilane, and commercially available products include "KBM-1003" and "KBE-1003" manufactured by Shin-Etsu Chemical Co., Ltd.

[0107] Examples of epoxy silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Commercially available products include "KBM-303," "KBM-402," "KBM-403," "KBE-402," and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

[0108] Examples of styryl-based silane coupling agents include p-styryltrimethoxysilane, and commercially available products include "KBM-1403" manufactured by Shin-Etsu Chemical Co., Ltd. Examples of (meth)acrylic-based silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, and commercially available products include "KBM-502", "KBM-503", "KBE-502", "KBE-503", and "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd.

[0109] Examples of isocyanurate-based silane coupling agents include tris-(trimethoxysilylpropyl)isocyanurate, and commercially available products include "KBM-9659" manufactured by Shin-Etsu Chemical Co., Ltd. Examples of ureido-based silane coupling agents include 3-ureidopropyltrialkoxysilane, and commercially available products include "KBE-585" manufactured by Shin-Etsu Chemical Co., Ltd.

[0110] Examples of mercapto-based silane coupling agents include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Examples of commercially available products include "KBM-802", "KBM-803", etc. manufactured by Shin-Etsu Chemical Co., Ltd. Examples of isocyanate-based silane coupling agents include 3-isocyanatopropyltriethoxysilane, etc. Examples of commercially available products include "KBE-9007N", etc. manufactured by Shin-Etsu Chemical Co., Ltd. Examples of acid anhydride-based silane coupling agents include 3-trimethoxysilylpropyl succinic anhydride, etc. Examples of commercially available products include "X-12-967C", etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0111] (D1) From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment of the inorganic filler having an average particle diameter of 20 nm to 90 nm with a surface treatment agent preferably falls within a predetermined range. Specifically, 100% by mass of the inorganic filler of (D1) is preferably surface-treated with 0.2% to 15% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 13% by mass, and even more preferably surface-treated with 0.3% to 10% by mass.

[0112] (D1) The degree of surface treatment of the inorganic filler having an average particle diameter of 20 nm to 90 nm with a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler having an average particle diameter of 20 nm to 90 nm in (D1) is preferably 0.02 mg / m 2 or more from the viewpoint of improving the dispersibility of the inorganic filler, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 [[ID=I8]]or less, and even more preferably 2 or less.

[0113] ​(D1) The amount of carbon per unit surface area of the inorganic filler with an average particle size of 20 nm to 90 nm can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0114] (D1) When the non-volatile components in the photosensitive resin composition are 100% by mass, the content of the inorganic filler with an average particle size of 20 nm to 90 nm is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and even more preferably 5% by mass or more. The upper limit is, for example, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0115] (D2) The inorganic filler with an average particle size of 100 nm to 500 nm preferably has an average particle size of 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, and even more preferably 250 nm or less. The lower limit of its average particle size is preferably 130 nm or more, and more preferably 150 nm or more.

[0116] (D2) The inorganic filler with an average particle size of 100 nm to 500 nm is not particularly limited, but the specific surface area is preferably 6 m 2 / g or more, more preferably 8 m 2 / g or more, still more preferably 10 m 2 / g or more. The upper limit of its specific surface area is not particularly limited, but is preferably 25 m 2 / g or less, more preferably 24 m 2 / g or less, still more preferably 23 m 2It is less than / g.

[0117] (D2) The inorganic filler having an average particle size of 100 nm to 500 nm preferably includes an inorganic filler that has been surface-treated with a surface treatment agent.

[0118] (D2) Examples of surface treatment agents for inorganic fillers having an average particle size of 100 nm to 500 nm include silane coupling agents such as amino silane coupling agents, vinyl silane coupling agents, epoxy silane coupling agents, styryl silane coupling agents, (meth)acrylic silane coupling agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents, and acid anhydride silane coupling agents.

[0119] (D2) The inorganic filler having an average particle size of 100 nm to 500 nm is more preferably an inorganic filler that has been surface-treated with a surface treatment agent selected from vinyl-based silane coupling agents and amino-based silane coupling agents, and is particularly preferably an inorganic filler that has been surface-treated with an amino-based silane coupling agent.

[0120] (D2) The degree of surface treatment with a surface treatment agent and the amount of carbon per unit surface area of ​​the inorganic filler with an average particle size of 100 nm to 500 nm may be the same as that of the inorganic filler with an average particle size of 20 nm to 90 nm (D1).

[0121] (D2) The content of inorganic fillers having an average particle size of 100 nm to 500 nm is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more, when the nonvolatile components in the photosensitive resin composition are considered to be 100% by mass. The upper limit is, for example, preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less.

[0122] The mass ratio ((D2) component / (D1) component) of the inorganic filler (D2) having an average particle size of 100 nm to 500 nm to the inorganic filler (D1) having an average particle size of 20 nm to 90 nm is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.5 or more, even more preferably 1 or more, and particularly preferably 1.5 or more. The upper limit of the mass ratio ((D2) / (D1)) is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less.

[0123] The mass ratio (100nm~500nm / 20nm~90nm) of inorganic fillers with particle sizes in the range of 100nm~500nm to inorganic fillers with particle sizes in the range of 20nm~90nm is preferably 0.1 or higher, more preferably 0.2 or higher, even more preferably 0.5 or higher, even more preferably 1 or higher, and particularly preferably 1.5 or higher. The upper limit of this mass ratio (100nm~500nm / 20nm~90nm) is preferably 50 or lower, more preferably 30 or lower, even more preferably 20 or lower, even more preferably 15 or lower, and particularly preferably 10 or lower.

[0124] (D) The content of inorganic filler is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more, when the nonvolatile components in the photosensitive resin composition are considered to be 100% by mass. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less, from the viewpoint of further improving developability.

[0125] <(E) Photosensitizer> The photosensitive resin composition of the present invention may further contain (E) a photosensitizer as an optional component. However, components corresponding to (C) a photopolymerization initiator are not included in (E) the photosensitizer. By including (E) a photosensitizer, the photocurability can be improved.

[0126] (E) The maximum absorption wavelength of the photosensitizer is preferably in the range of 300 nm to 450 nm, more preferably in the range of 330 nm to 420 nm, and particularly preferably in the range of 350 nm to 400 nm.

[0127] (E) The lowest excited triplet energy level of the photosensitizer is preferably 60 kcal / mol to 70 kcal / mol, more preferably 60 kcal / mol to 65 kcal / mol, and particularly preferably 60 kcal / mol to 63 kcal / mol.

[0128] (E)Specific examples of photosensitizers include thioxanthenes, thioxanthones, benzophenones, anthraquinones, etc. (E)The photosensitizer preferably includes a photosensitizer selected from thioxanthones and benzophenones.

[0129] Examples of thioxanthenes include thioxanthene, 2-chlorothioxanthene, and 2,4-diethylthioxanthene. Examples of thioxanthones include 2,4-diethylthioxanthene-9-one, 2-isopropylthioxanthene-9-one, 1-isopropylthioxanthene-9-one, and 2,4-diisopropylthioxanthene-9-one. Examples of benzophenones include benzophenone, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, o-methyl benzoylbenzoate, and 4-methylbenzophenone. Examples of anthraquinones include 2-ethylanthraquinone, 1-chloroanthraquinone, and 2,3-diphenylanthraquinone.

[0130] (E) The content of the photosensitizer is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, when the nonvolatile components of the photosensitive resin composition are considered to be 100% by mass, from the viewpoint of further improving photocurability. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less.

[0131] <(F) Reactive Diluent> The photosensitive resin composition may further contain (F) a reactive diluent as an optional component. However, components corresponding to (A) epoxy resin, (B) acid-modified epoxy (meth)acrylate resin, and (C) photopolymerization initiator are not included in (F) the reactive diluent. By including (F) the reactive diluent in the photosensitive resin composition, the photoreactivity can be improved. As (F) the reactive diluent, for example, a (meth)acrylate compound having one or more (preferably two or more) (meth)acryloyl groups per molecule can be used. (F) The reactive diluent may be used alone or in combination of two or more types.

[0132] Examples of typical photosensitive (meth)acrylate compounds include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or polyhydric acrylates of adducts thereof to ethylene oxide, propylene oxide, or ε-caprolactone; phenols such as phenoxyacrylate and phenoxyethyl acrylate, or acrylates of their ethylene oxide or propylene oxide adducts; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; modified epoxy acrylates; melamine acrylates; and / or methacrylates corresponding to the above acrylates.Among these, polyvalent acrylates or polyvalent methacrylates are preferred. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and dipentaerythritol Examples include trivalent (meth)acrylates such as hexa(meth)acrylate and N,N,N',N'-tetrakis(β-hydroxyethyl)ethyldiamine (meth)acrylic acid esters. Examples of trivalent or higher acrylates or methacrylates include phosphate triester (meth)acrylates such as tri(2-(meth)acryloyloxyethyl) phosphate, tri(2-(meth)acryloyloxypropyl) phosphate, tri(3-(meth)acryloyloxypropyl) phosphate, tri(3-(meth)acryloyl-2-hydroxyloxypropyl) phosphate, di(3-(meth)acryloyl-2-hydroxyloxypropyl)(2-(meth)acryloyloxyethyl) phosphate, and (3-(meth)acryloyl-2-hydroxyloxypropyl)di(2-(meth)acryloyloxyethyl) phosphate. These photosensitive (meth)acrylate compounds may be used individually or in combination of two or more. "EO" refers to ethylene oxide.

[0133] (F) A commercially available reaction diluent may be used. Examples of commercially available products include "DPHA" manufactured by Nippon Kayaku Co., Ltd. and "EBECRYL3708" manufactured by Daicel Ornex Co., Ltd.

[0134] (F) As for the content of the reaction diluent, when the nonvolatile components in the photosensitive resin composition are considered to be 100% by mass, from the viewpoint of promoting photocuring, it is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 7% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, particularly preferably 25% by mass or less, and 20% by mass or less.

[0135] <(G) Organic Solvents> The photosensitive resin composition may further contain (G) an organic solvent as an optional component. The viscosity of the varnish can be adjusted by including component (G). Examples of organic solvents (G) include ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diglycol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These can be used individually or in combination of two or more. When using organic solvents, their content can be appropriately adjusted from the viewpoint of the coatability of the photosensitive resin composition.

[0136] (G) The content of the organic solvent is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less, when the total components in the photosensitive resin composition are considered to be 100% by mass. The lower limit may be 1% by mass or more, 10% by mass or more, etc.

[0137] <(H) Other additives> The photosensitive resin composition may further contain (H) and other additives to an extent that does not hinder the objectives of the present invention. Examples of (H) and other additives include other photopolymerization initiators, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, carbon black, and naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, thickeners such as bentonite and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoamers, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters, thermosetting resins such as phenolic curing agents and cyanate ester curing agents.

[0138] <Method for producing a photosensitive resin composition> The photosensitive resin composition of the present invention can be manufactured by appropriately mixing each component and, if necessary, kneading or stirring using a kneading means such as a three-roll mill, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer, planetary mixer, or high-speed rotary mixer.

[0139] <Physical properties of photosensitive resin compositions> The photosensitive resin composition of the present invention has the properties of having excellent resolution, suppressing the occurrence of connection failures in reduced-diameter via holes, and enabling the formation of an insulating layer with superior copper plating peel strength.

[0140] The photosensitive resin composition of the present invention has excellent resolution, and in one embodiment, it may have the characteristic of having a smaller minimum aperture diameter (minimum via diameter) of via holes that can be formed when exposure and development are performed. Therefore, in one embodiment, the minimum aperture diameter observed as in Test Example 2 below may be preferably 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, and particularly preferably less than 50 μm. The lower limit is not particularly limited, but may be 1 μm or more, for example.

[0141] The cured product of the photosensitive resin composition of the present invention may have the characteristic of having a higher peel strength (copper plating peel strength / adhesion) from the copper-plated conductor layer. Therefore, in one embodiment, the peel strength of the cured product of the photosensitive resin composition of the present invention from the copper-plated conductor layer, when measured as in Test Example 5 below, may preferably be 0.3 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but for example, it may be 10 kgf / cm or less.

[0142] The photosensitive resin composition of the present invention may have the characteristic of less exposure of inorganic filler and a smoother surface on the wall surface of via holes (exposure-developing apertures / laser apertures) after roughening treatment, as evaluated as shown in Test Examples 2 and 3 below. The photosensitive resin composition of the present invention may have the characteristic of less exposure of inorganic filler and a smoother surface on the resist surface above via holes (exposure-developing apertures / laser apertures) after roughening treatment, as evaluated as shown in Test Examples 2 and 3 below. The photosensitive resin composition of the present invention may have the characteristic of no detachment of inorganic filler at the bottom of via holes (exposure-developing apertures / laser apertures) after roughening treatment, as evaluated as shown in Test Examples 2 and 3 below.

[0143] In one embodiment, the photosensitive resin composition of the present invention can form via holes with more suppressed undercutting when exposed to light and developed, i.e., via holes with a shape in which the difference between the radius of the top and the radius of the bottom is smaller or nonexistent. Therefore, in one embodiment, as shown in Test Example 2 below, a via hole with an opening diameter of 50 μm is formed, and the radius of the top (μm) and the radius of the bottom (μm) of the cross-section are measured by SEM, and the undercut obtained by calculating the difference between the radius of the top and the radius of the bottom (radius of the top - radius of the bottom) can preferably be 15 μm or less, more preferably 10 μm or less, even more preferably 6 μm or less, and even more preferably less than 3 μm, and particularly preferably no undercut (0 μm). The evaluation of undercutting can be measured according to the method described in the examples below.

[0144] In one embodiment, the cured product of the photosensitive resin composition of the present invention may have the characteristic of having a lower arithmetic mean roughness (Ra) after roughening treatment. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the cured product of the photosensitive resin composition of the present invention, when measured as in Test Example 4 below, is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably less than 200 nm. The lower limit is not particularly limited, but may be 1 nm or more.

[0145] In one embodiment, the cured product of the photosensitive resin composition of the present invention may have the characteristic of being able to suppress warping. Therefore, in one embodiment, the amount of warping in the short-side direction measured as in Test Example 6 below may preferably be less than 10 μm.

[0146] In one embodiment, the cured product of the photosensitive resin composition of the present invention may have the characteristic of having a lower mean linear thermal expansion coefficient (CTE). Therefore, in one embodiment, the mean linear thermal expansion coefficient (CTE) of the cured product of the photosensitive resin composition of the present invention, when measured as in Test Example 1 below, is preferably 100 ppm or less, more preferably 60 ppm or less, even more preferably 50 ppm or less, and particularly preferably less than 40 ppm. The lower limit is not particularly limited, but may be 10 ppm or more.

[0147] <Uses of photosensitive resin compositions> The applications of the photosensitive resin composition of the present invention are not particularly limited, but it can be used in a wide range of applications where a photosensitive resin composition is required, such as photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminate applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component embedding resins. In particular, it can be suitably used as a photosensitive resin composition for the insulating layer of a printed wiring board (a printed wiring board using a cured product of the photosensitive resin composition as the insulating layer), a photosensitive resin composition for the interlayer insulating layer (a printed wiring board using a cured product of the photosensitive resin composition as the interlayer insulating layer (interlayer insulating material)), a photosensitive resin composition for plating formation (a printed wiring board on which plating is formed on a cured product of the photosensitive resin composition), and a photosensitive resin composition for solder resist formation (a printed wiring board using a cured product of the photosensitive resin composition as the solder resist).

[0148] <Photosensitive film with support> The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support, in which the photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support comprises a support and a photosensitive resin composition layer formed on the support using the photosensitive resin composition of the present invention.

[0149] Examples of support materials include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl acetate film, with polyethylene terephthalate film being particularly preferred.

[0150] Examples of commercially available supports include, but are not limited to, polypropylene films such as "Alfan MA-410" and "E-200C" from Oji Paper Co., Ltd., and polyethylene terephthalate films such as the PS series "PS-25" from Teijin Corporation. These supports are preferably coated with a release agent such as a silicone coating agent on their surface to facilitate the removal of the photosensitive resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. A thickness of 5 μm or more can suppress tearing of the support when peeling it off before development, and a thickness of 50 μm or less can improve the resolution when exposing the support. Furthermore, a low-fisheye support is preferred. Here, "fisheye" refers to the incorporation of foreign matter, undissolved material, oxidized degradation products, etc., into the film when the material is heat-melted, kneaded, extruded, biaxially stretched, cast, etc.

[0151] Furthermore, in order to reduce light scattering during exposure by active light such as ultraviolet rays, the support material is preferably one with excellent transparency. Specifically, the support material is preferably one with a turbidity (haze, as standardized in JIS-K6714), which is an indicator of transparency, of 0.1 to 5. In addition, the photosensitive resin composition layer may be protected by a protective film.

[0152] By protecting the photosensitive resin composition layer of the photosensitive film with a support with a protective film, it is possible to prevent dust and other debris from adhering to the surface of the photosensitive resin composition layer and to prevent scratches. The protective film can be made of the same material as the support described above. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. A thickness of 1 μm or more improves the handling of the protective film, while a thickness of 40 μm or less tends to improve cost-effectiveness. It is preferable that the adhesive strength between the photosensitive resin composition layer and the protective film is less than the adhesive strength between the photosensitive resin composition layer and the support.

[0153] A photosensitive film with a support can be manufactured, for example, by applying the photosensitive resin composition of the present invention, either as is or dissolved in an organic solvent to form a varnish, onto a support, and then drying the organic solvent by heating or hot air blowing to form a photosensitive resin composition layer. Specifically, a photosensitive film with a support can be manufactured by first completely removing bubbles from the photosensitive resin composition using a vacuum degassing method, then applying the photosensitive resin composition onto a support, removing the solvent using a hot air furnace or far-infrared furnace, drying it, and then, if necessary, laminating a protective film onto the resulting photosensitive resin composition layer. The specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin composition, but for a resin composition containing 30% to 60% by mass of organic solvent, it can be dried at 80°C to 120°C for 3 to 13 minutes. The amount of residual organic solvent in the photosensitive resin composition layer after drying is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total amount of the photosensitive resin composition layer, in order to prevent the diffusion of organic solvent in subsequent processes. Those skilled in the art can appropriately set suitable drying conditions through simple experiments.

[0154] The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, even more preferably in the range of 10 μm to 150 μm, even more preferably in the range of 10 μm to 100 μm, particularly preferably in the range of 10 μm to 60 μm, and especially preferably in the range of 10 μm to 30 μm, from the viewpoint of improving handling and suppressing a decrease in sensitivity and resolution inside the photosensitive resin composition layer.

[0155] Examples of coating methods for photosensitive resin compositions include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spray coating, and dip coating.

[0156] The photosensitive resin composition may be applied in several stages, in a single stage, or by combining multiple different methods. Among these, the die-coating method is preferred because it offers excellent uniformity. Furthermore, to avoid contamination with foreign matter, it is preferable to carry out the coating process in an environment with minimal foreign matter generation, such as a cleanroom.

[0157] <Printed wiring board> The printed circuit board of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

[0158] In detail, the printed circuit board of the present invention can be manufactured using the above-described photosensitive film with support. The following describes the case where the insulating layer is solder resist.

[0159] <Laminating and drying process> A photosensitive resin composition layer is formed on a circuit board by laminating the photosensitive resin composition layer side of a photosensitive film with a support onto a circuit board and drying it.

[0160] Examples of circuit boards include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Here, a circuit board refers to a substrate on which a patterned conductive layer (circuit) is formed on one or both sides of the substrate as described above. Furthermore, a multilayer printed wiring board, which is formed by alternately laminating conductive layers and insulating layers, is also included in the definition of a circuit board in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductive layers (circuits). The surface of the conductive layer may be pre-treated to roughen it by blackening, copper etching, or the like.

[0161] In one embodiment of the lamination process, the photosensitive resin composition layer is laminated to one or both sides of the circuit board using a vacuum laminator. In the lamination process, if the photosensitive film with support has a protective film, the protective film is removed, and then, if necessary, the photosensitive film with support and the circuit board are preheated, and the photosensitive resin composition layer is pressed onto the circuit board while applying pressure and heating. For the photosensitive film with support, a method of laminating it to the circuit board under reduced pressure using a vacuum lamination method is preferably used.

[0162] The conditions for the lamination process are not particularly limited, but for example, the bonding temperature (lamination temperature) is preferably 70°C to 140°C, and the bonding pressure is preferably 1 kgf / cm². 2 ~11 kgf / cm² 2 (9.8 × 10 4 N / m 2 ~107.9×10 4 N / m 2The lamination process is preferably carried out under reduced pressure, with a pressing time of 5 to 300 seconds and an air pressure of 20 mmHg (26.7 hPa) or less. The lamination process may be batch-type or continuous-type using rolls. The vacuum lamination method can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the vacuum applicator manufactured by Nikko Materials, the vacuum pressure laminator manufactured by Meiki Seisakusho, the roll-type dry coater manufactured by Hitachi Industries, and the vacuum laminator manufactured by Hitachi AIC. In this way, a photosensitive film with a support is formed on the circuit board.

[0163] Instead of laminating a photosensitive film with a support, a photosensitive resin composition layer may be formed on the circuit board by directly applying the photosensitive resin composition to the circuit board and drying the organic solvent. While full-surface printing by screen printing is commonly used as the application method, any other application method that can provide uniform application may be used. For example, spray coating, hot melt coating, bar coating, applicator coating, blade coating, knife coating, air knife coating, curtain flow coating, roll coating, gravure coating, offset printing, dip coating, brush application, and all other conventional application methods can be used. After application, drying is performed as needed using a hot air oven or far-infrared oven. The drying conditions are preferably 80°C to 120°C for 3 to 13 minutes.

[0164] <Exposure process> After a photosensitive resin composition layer is formed on the circuit board by the above process, an exposure process is performed in which an active light is irradiated onto a predetermined portion of the photosensitive resin composition layer through a mask pattern to photo-cure the photosensitive resin composition layer in the irradiated area. Examples of active light include ultraviolet light, visible light, electron beams, and X-rays, with ultraviolet light being particularly preferred. The irradiation dose of ultraviolet light is approximately 10 mJ / cm². 2 ~1000 mJ / cm 2There are two methods of exposure: contact exposure, in which the mask pattern is brought into close contact with the printed circuit board, and non-contact exposure, in which the mask pattern is exposed using parallel light without contact. Either method may be used. Furthermore, if a support is present on the photosensitive resin composition layer, exposure may be performed from the support, or the support may be removed before exposure.

[0165] Because the solder resist uses the photosensitive resin composition of the present invention, it exhibits excellent developability (resolution). Therefore, as exposure patterns in the mask pattern, for example, patterns with a ratio of circuit width (line; L) to the width between circuits (space; S) (L / S) of 100 μm / 100 μm or less (i.e., wiring pitch of 200 μm or less), L / S = 80 μm / 80 μm or less (wiring pitch of 160 μm or less), L / S = 70 μm / 70 μm or less (wiring pitch of 140 μm or less), and L / S = 60 μm / 60 μm or less (wiring pitch of 120 μm or less) can be used. Note that the pitch does not need to be the same throughout the entire circuit board.

[0166] <Developing process> After the exposure process, if a support is present on the photosensitive resin composition layer, the support is removed, and then the uncured parts (unexposed areas) are removed by wet development or dry development to form a pattern.

[0167] In the wet development described above, a safe, stable, and easy-to-handle developer such as an alkaline aqueous solution, a water-based developer, or an organic solvent is used as the developer, with the alkaline aqueous solution being particularly preferred. Furthermore, known methods such as spraying, swirling immersion, brushing, and scraping can be appropriately employed as the development method.

[0168] Examples of alkaline aqueous solutions used as developing solutions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates or alkali metal bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; aqueous solutions of organic bases such as tetraalkylammonium hydroxide; or aqueous solutions of these.

[0169] These alkaline aqueous solutions may contain surfactants, defoamers, and the like to improve the developing effect. The pH of the alkaline aqueous solution is preferably in the range of 8 to 12, and more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0170] Organic solvents used as developing solutions include, for example, acetone, ethyl acetate, alkoxyethanol having alkoxy groups with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0171] The concentration of such organic solvents is preferably 2% to 90% by mass relative to the total volume of the developer. The temperature of such organic solvents can be adjusted according to the developing properties. Furthermore, such organic solvents can be used alone or in combination of two or more types. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0172] In pattern formation, two or more of the above-described development methods may be used in combination as needed. Development methods include the dip method, battle method, spray method, high-pressure spray method, brushing, and slapping, with the high-pressure spray method being preferable for improving resolution. When using the spray method, a spray pressure of 0.05 MPa to 0.3 MPa is preferred.

[0173] <Thermosetting (post-bake) process> After the development process described above is completed, a heat-curing (post-bake) process is performed to form solder resist. Post-bake processes include UV irradiation using a high-pressure mercury lamp and heating using a clean oven. When UV irradiation is used, the irradiation dose can be adjusted as needed, for example, to 0.05 J / cm². 2 ~10J / cm 2 Irradiation can be performed with a moderate irradiation dose. The heating conditions can be appropriately selected depending on the type and content of the resin components in the photosensitive resin composition, but preferably they are selected in the range of 150°C to 220°C for 20 minutes to 180 minutes, and more preferably in the range of 160°C to 200°C for 30 minutes to 120 minutes.

[0174] <Other processes> The printed circuit board may further include a drilling process and a desmear process after the solder resist has been formed. These processes may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed circuit boards.

[0175] After forming the solder resist, via holes and through holes are formed in the solder resist on the circuit board, if desired. The drilling process can be carried out by known methods such as drills, lasers, and plasma, or a combination of these methods as needed, but drilling by lasers such as carbon dioxide lasers and YAG lasers is preferred.

[0176] The desmearing process is a process for removing desmear. Generally, resin residue (smear) adheres to the inside of the opening formed in the drilling process. Since this smear can cause electrical connection problems, a process to remove the smear (desmearing) is carried out in this step.

[0177] Desmear treatment may be carried out by dry desmear treatment, wet desmear treatment, or a combination thereof.

[0178] Examples of dry desmearing processes include plasma-based desmearing. Plasma-based desmearing can be performed using commercially available plasma desmearing equipment. Among commercially available plasma desmearing equipment, examples suitable for printed circuit board manufacturing include microwave plasma equipment manufactured by Nissin Corporation and atmospheric pressure plasma etching equipment manufactured by Sekisui Chemical Co., Ltd.

[0179] Examples of wet desmear treatments include desmear treatment using an oxidizing agent solution. When desmear treatment is performed using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing solution in this order. Examples of swelling solutions include "Swelling-Dip-Securigant P" and "Swelling-Dip-Securigant SBU" manufactured by Atotec Japan. The swelling treatment is preferably performed by immersing the substrate, which has via holes formed on it, in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. As an oxidizing agent solution, an alkaline permanganate aqueous solution is preferred, for example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dozing Solution Securigant P" from Atotech Japan. Neutralization treatment with a neutralizing solution is preferably carried out by immersing the oxidized substrate in a neutralizing solution at 30°C to 50°C for 3 to 10 minutes. An acidic aqueous solution is preferred as the neutralizing solution, and an example of a commercially available product is "Reduction Solution Securigant P" from Atotech Japan.

[0180] When combining dry desmearing and wet desmearing, the dry desmearing may be performed first, or the wet desmearing may be performed first.

[0181] When the insulating layer is used as an interlayer insulating layer, the process can be carried out in the same way as with solder resist, and after the heat curing process, drilling, desmearing, and plating processes may be performed.

[0182] The plating process is a process of forming a conductive layer on an insulating layer. The conductive layer may be formed by a combination of electroless plating and electrolytic plating, or a plating resist with a pattern inverse to that of the conductive layer may be formed, and the conductive layer may be formed by electroless plating alone. As a method for subsequent pattern formation, for example, subtractive methods and semi-additive methods known to those skilled in the art can be used.

[0183] <Semiconductor device> The semiconductor device of the present invention includes a printed circuit board. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

[0184] Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

[0185] The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on conductive locations on a printed circuit board. A "conductive location" is a "location on the printed circuit board that transmits electrical signals," and this location may be on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor material.

[0186] The method for mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, examples include wire bonding mounting methods, flip-chip mounting methods, mounting methods using bumpless build-up layers (BBUL), mounting methods using anisotropic conductive films (ACF), and mounting methods using non-conductive films (NCF). Here, "mounting method using bumpless build-up layers (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed circuit board and the semiconductor chip is connected to the wiring on the printed circuit board." [Examples]

[0187] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "mass%", respectively, unless otherwise specified. Unless a temperature is specifically specified, the temperature condition is room temperature (23°C), and unless a pressure is specifically specified, the pressure condition is atmospheric pressure (1 atm). The weight-average molecular weight is the weight-average molecular weight in polystyrene terms measured by gel permeation chromatography.

[0188] <Synthesis Example 1: Synthesis of Naphthol Aralkyl Skeleton-Containing Ester-Type Acid-Modified Epoxyacrylate Resin> 325 parts of epoxy resin having a naphthol aralkyl skeleton ("ESN-475V", manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent of 325 g / eq.) were placed in a flask equipped with a gas inlet tube, stirrer, condenser, and thermometer. 340 parts of carbitol acetate were added and heated until dissolved. 0.46 parts of hydroquinone and 1 part of triphenylphosphine were then added. This mixture was heated to 95-105°C, and 72 parts of acrylic acid were gradually added dropwise, reacting for 16 hours. The reaction product was cooled to 80-90°C, 80 parts of tetrahydrophthalic anhydride were added, reacted for 8 hours, and then cooled. The amount of solvent was adjusted to obtain a resin solution (non-volatile content 70%) with an acid value of 60 mg KOH / g of solids. The weight-average molecular weight of naphthol aralkyl type epoxy acrylate (1000) was 1000.

[0189] <Example 1> 10 parts of naphthol aralkyl epoxy resin (ESN-475V, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.), 25 parts of naphthol aralkyl skeleton-containing ester-type acid-modified epoxy acrylate resin (non-volatile content 70%) obtained in Synthesis Example 1, 3 parts of fluorenyl group-containing aminoketone-based photopolymerization initiator (TR-NPI-20400, manufactured by TRONLY, 2-methyl-1-(9,9-dibutylfluoren-2-yl)-2-morpholinopropan-1-one), and spherical silica (Y50SZ-AM1, manufactured by Admatex Co., Ltd., specific surface area 60 m²) surface-treated with an amino-based silane coupling agent (KBM5783, manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminooctyltrimethoxysilane). 2 15 parts of ( / g, average particle size 0.05 μm, solid content 50%), and spherical silica (Admatex Corporation's "180nmSX-C1", specific surface area 20 m²) surface-treated with an amino-based silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM5783", N-phenyl-3-aminooctyltrimethoxysilane). 2 A varnish-like photosensitive resin composition was prepared by mixing 40 parts of ( / g, average particle size 0.2 μm), 0.3 parts of photosensitizer (DETX-S manufactured by Nippon Kayaku Co., Ltd.), 0.3 parts of photosensitizer (EAB manufactured by Tokyo Chemical Industry Co., Ltd.), 10 parts of reactive diluent (DPHA manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate), 1 part of ethyl diglycol acetate, and 10 parts of methyl ethyl ketone, and using a high-speed rotary mixer.

[0190] <Example 2> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "Y50SZ-AM1", specific surface area 60 m²) 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount used ( / g, average particle size 0.05 μm, solid content 50%) was changed from 15 parts to 25 parts.

[0191] <Example 3> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "Y50SZ-AM1", specific surface area 60 m²) 2A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount used ( / g, average particle size 0.05 μm, solid content 50%) was changed from 15 parts to 40 parts.

[0192] <Example 4> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "180nmSX-C1", specific surface area 20m²) 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount used ( / g, average particle size 0.2 μm) was changed from 40 parts to 30 parts.

[0193] <Example 5> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "180nmSX-C1", specific surface area 20m²) 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount used ( / g, average particle size 0.2 μm) was changed from 40 parts to 60 parts.

[0194] <Example 6> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 40 parts of a biphenyl skeleton-containing ester-type acid-modified epoxy acrylate resin (ZCR-8001H, manufactured by Nippon Kayaku Co., Ltd., with a non-volatile content of 65%) were used instead of 25 parts of the naphthol aralkyl skeleton-containing ester-type acid-modified epoxy acrylate resin (non-volatile content of 70%) obtained in Synthesis Example 1.

[0195] <Example 7> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 parts of biphenyl-type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288 g / eq.) were used instead of 10 parts of naphthol aralkyl-type epoxy resin (ESN-475V, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.).

[0196] <Example 8> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "180nmSX-C1", specific surface area 20m²) 2 Spherical silica (Admatex Corporation's "K180SV-C2", specific surface area 20 m²) surface-treated with a vinylsilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-1003", vinyltrimethoxysilane) instead of 40 parts (average particle size 0.2 μm / g). 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 40 parts (1 / g, average particle size 0.2 μm) were used.

[0197] <Example 9> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 5 parts of a phosphine oxide-based photopolymerization initiator (Omnipol TP, polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphine]) were used instead of 3 parts of a fluorene skeleton-containing aminoketone-based photopolymerization initiator (TR-NPI-20400, TRONLY).

[0198] <Example 10> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 2 parts of a phosphine oxide-based photopolymerization initiator (Omnirad 819, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by IGM) were used instead of 3 parts of a fluorene skeleton-containing aminoketone-based photopolymerization initiator (TR-NPI-20400, manufactured by TRONLY).

[0199] <Comparative Example 1> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "180nmSX-C1", specific surface area 20m²) 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 40 parts ( / g, average particle size 0.2 μm) were not used.

[0200] <Comparative Example 2> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "Y50SZ-AM1", specific surface area 60 m²) 2 15 parts of ( / g, average particle size 0.05 μm, solid content 50%) were not used, and spherical silica (Admatex "180nmSX-C1", specific surface area 20 m²) surface-treated with an amino-based silane coupling agent was not used. 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount used ( / g, average particle size 0.2 μm) was changed from 40 parts to 60 parts.

[0201] <Comparative Example 3> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "Y50SZ-AM1", specific surface area 60 m²) 2 Instead of 15 parts of ( / g, average particle size 0.05 μm, solid content 50%), spherical silica (Admatex Corporation's "Y50SV-AM1", specific surface area 60 m²) surface-treated with a vinylsilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-1003", vinyltrimethoxysilane) was used. 2 15 parts of (1 / g, average particle size 0.05 μm, solid content 50%) were used, and spherical silica (Admatex "180nmSX-C1", specific surface area 20 m²) surface-treated with an amino-based silane coupling agent was used. 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 40 parts ( / g, average particle size 0.2 μm) were not used.

[0202] <Comparative Example 4> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "Y50SZ-AM1", specific surface area 60 m²) 2 Instead of 15 parts of ( / g, average particle size 0.05 μm, solid content 50%), spherical silica (Admatex Corporation's "Y50SV-AM1", specific surface area 60 m²) surface-treated with a vinylsilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-1003", vinyltrimethoxysilane) was used. 2 15 parts of (1 / g, average particle size 0.05 μm, solid content 50%) were used, and spherical silica (Admatex "180nmSX-C1", specific surface area 20 m²) surface-treated with an amino-based silane coupling agent was used.2 Spherical silica (Admatex Corporation's "K180SV-C2", specific surface area 20 m²) surface-treated with a vinylsilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-1003", vinyltrimethoxysilane) instead of 40 parts (average particle size 0.2 μm / g). 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 40 parts (1 / g, average particle size 0.2 μm) were used.

[0203] <Comparative Example 5> Spherical silica surface-treated with an amino-based silane coupling agent (Admatex "Y50SZ-AM1", specific surface area 60 m²) 2 Instead of 15 parts of ( / g, average particle size 0.05 μm, solid content 50%), spherical silica (Admatex Corporation's "Y50SV-AM1", specific surface area 60 m²) surface-treated with a vinylsilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-1003", vinyltrimethoxysilane) was used. 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 15 parts of (1 / g, average particle size 0.05 μm, solid content 50%) were used.

[0204] <Test Example 1: Evaluation of the mean linear thermal expansion coefficient> As a support, a PET film (Toray Industries, Ltd., "Lumirror T6AM", thickness 38 μm, softening point 130°C, "Release PET") treated with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared. The varnish-like photosensitive resin compositions obtained in the examples and comparative examples were uniformly applied to the prepared release PET using a die coater so that the thickness of the photosensitive resin composition layer after drying was 20 μm (for the photosensitive resin composition of Example 1, in addition to the 20 μm thickness, a 40 μm thickness was also prepared), and dried at 80°C to 110°C for 6 minutes to obtain a support-attached photosensitive film having a photosensitive resin composition layer on the release PET.

[0205] The photosensitive resin composition layer of the resulting photosensitive film with support was treated with 2 J / cm² of resin. 2The material was irradiated with ultraviolet light and then heated at 170°C for 1 hour to obtain a cured product. After that, the support was peeled off to obtain cured product A for evaluation.

[0206] The cured material A for evaluation was cut into test specimens with a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed using a thermomechanical analyzer (Rigaku Corporation, Thermo Plus, TMA8310) with the tensile loading method. After mounting the test specimens in the apparatus, measurements were taken twice consecutively under measurement conditions of a load of 1 g and a heating rate of 5 °C / min. The average linear thermal expansion coefficient (ppm) from 25 °C to 150 °C in the second measurement was calculated and evaluated according to the following evaluation criteria.

[0207] (Evaluation criteria for mean linear thermal expansion coefficient) "〇": Mean linear thermal expansion coefficient is less than 40 ppm "△": Mean linear thermal expansion coefficient is between 40 ppm and 60 ppm. "×": Mean linear thermal expansion coefficient exceeds 60 ppm

[0208] <Test Example 2: Evaluation of Resolution and Via Hole by Exposure> A copper layer on a glass epoxy substrate (copper-clad laminate) with a patterned copper layer 18 μm thick was roughened by treatment with an organic acid-containing surface treatment agent (CZ8100, manufactured by MEC). Next, a photosensitive film with a support, similar to that obtained in Test Example 1, was placed so that the photosensitive resin composition layer was in contact with the copper circuit surface, and laminated using a vacuum laminator (Nikko Materials Co., Ltd., VP160) to produce an evaluation laminate A in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The bonding conditions were a vacuum time of 30 seconds, a bonding temperature of 80°C, a bonding pressure of 0.7 MPa, and a pressing time of 30 seconds. After producing the evaluation laminate A, it was left to stand at room temperature (25°C) for 30 minutes or more.

[0209] Using a pattern forming apparatus, ultraviolet exposure was performed on the support of the evaluation laminate A using a 41-step tablet and a round hole pattern. The exposure pattern used a quartz glass mask that drew round holes with apertures of 40 μm / 50 μm / 60 μm / 70 μm / 80 μm / 90 μm / 100 μm. After standing at room temperature for 30 minutes, the support was peeled off from the evaluation laminate A. A 1 mass% aqueous sodium carbonate solution at 30 °C was sprayed as a developer on the entire surface of the photosensitive resin composition layer on the evaluation laminate A at a spray pressure of 0.2 MPa for 1 minute for spray development. After spray development, ultraviolet irradiation of 2 J / cm 2 was performed, and further heat treatment at 170 °C for 1 hour was performed to cure the photosensitive resin composition layer.

[0210] The exposure energy amount at which the number of remaining gloss steps of the 41-step tablet became 8 was defined as the sensitivity of the photosensitive resin composition. The round holes formed by patterning on the evaluation laminate A exposed at this sensitivity were observed by SEM (magnification 1000 times), and the minimum via hole diameter (minimum opening diameter) without residue or peeling was observed and evaluated according to the following evaluation criteria.

[0211] (Evaluation criteria for the minimum via hole diameter (minimum opening diameter)) “〇”: The minimum via hole diameter (minimum opening diameter) is less than 50 μm “△”: The minimum via hole diameter (minimum opening diameter) is 50 μm or more and 60 μm or less “×”: There is no minimum via hole diameter (minimum opening diameter) of 60 μm or less

[0212] Regarding the observation of undercut, vias with a via hole diameter of 50 μm were also observed by SEM (magnification 1000 times). The radius (μm) at the top and the radius (μm) at the bottom of the cross-section of the via hole with an opening diameter of 50 μm were measured by SEM, and the difference between the radius at the bottom and the radius at the top (radius at the bottom - radius at the top) was obtained, and the obtained value was defined as the undercut and evaluated according to the following evaluation criteria.

[0213] (Evaluation criteria for undercut) “◎”: There is no undercut 「〇」: Undercut is less than 3 μm 「△」: Undercut is 3 μm or more and 6 μm or less 「×」: Undercut is greater than 6 μm, or a via hole with a diameter of 50 μm is not open

[0214] Also, the following roughening treatment was performed on the evaluation laminate A. It was immersed in swelling dip·security gun P containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd., which is a swelling liquid, at 60 °C for 10 minutes. Next, as a roughening liquid, it was immersed in concentrate·compact P manufactured by Atotech Japan Co., Ltd. (an aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) at 80 °C for 10 minutes. Finally, as a neutralizing liquid, it was immersed in reduction solution·security gun P manufactured by Atotech Japan Co., Ltd. at 40 °C for 5 minutes. Regarding the evaluation of the resolution after desmear, the via holes were also observed (at a magnification of 1000 times) by SEM, similar to the observation of the minimum via hole diameter and undercut.

[0215] The wall surface of the via hole, the resist surface at the upper part of the via hole, and the state of the bottom of the via hole after desmear (roughening treatment) were evaluated according to the following evaluation criteria.

[0216] (Evaluation criteria for the wall surface of the via hole after desmear) 「〇」: There is little exposure of the inorganic filler on the wall surface of the via hole, and it is smooth. 「×」: There is a lot of exposure of the inorganic filler on the wall surface of the via hole, and it is uneven.

[0217] (Evaluation criteria for the resist surface at the upper part of the via hole after desmear) 「〇」: There is little exposure of the inorganic filler on the resist surface at the upper part of the via hole, and it is smooth. 「×」: There is a lot of exposure of the inorganic filler on the resist surface at the upper part of the via hole, and it is uneven.

[0218] (Evaluation criteria for the bottom of the via hole after desmear) 「〇」: There is no脱落 of the inorganic filler at the bottom of the via hole. "×": There is some detachment of inorganic filler material at the bottom of the beer hall.

[0219] <Test Example 3: Evaluation of via holes using laser aperture> Ultraviolet exposure was performed on the support of evaluation laminate A using a pattern forming apparatus at an exposure energy that resulted in 8 remaining glossy steps on a 41-step tablet. A quartz glass mask without an exposure pattern was used. After standing at room temperature for 30 minutes, the support was peeled off evaluation laminate A. The entire surface of the photosensitive resin composition layer on evaluation laminate A was spray-developed with a 1% by mass aqueous sodium carbonate solution at 30°C at a spray pressure of 0.2 MPa for 1 minute. After spray development, the yield was 2 J / cm². 2 The photosensitive resin composition layer was cured by irradiating it with ultraviolet light and then heating it at 170°C for 1 hour. Subsequently, a 25 μm circular hole was opened using a UV laser.

[0220] The roughening treatment was performed using the same method as that used for evaluation laminate A in Test Example 2.

[0221] The condition of the via hole walls, the resist surface above the via hole, and the bottom of the via hole after desmearing (roughening treatment) was evaluated according to the following criteria.

[0222] (Evaluation criteria for the walls of the beer hall after Desmear) "〇": The walls of the beer hall have minimal exposure of inorganic filler material and are smooth. "×": The walls of the beer hall have many exposed inorganic fillers, resulting in an uneven surface.

[0223] (Evaluation criteria for the resist surface above the via hole after desmearing) "〇": The resist surface above the via hole has minimal exposure of inorganic filler material and is smooth. "×": The resist surface above the via hole has a lot of exposed inorganic filler material, resulting in an uneven surface.

[0224] (Evaluation criteria for the bottom of the beer hall after Desmear) "〇": No inorganic filler material has fallen off the bottom of the beer hall. "×": There is some detachment of inorganic filler material at the bottom of the beer hall.

[0225] <Test Example 4: Evaluation of Arithmetic Mean Roughness> Using a pattern forming apparatus, ultraviolet exposure was performed on the support of evaluation laminate A, similar to that prepared in Test Example 2, at an exposure energy that resulted in 8 remaining glossy steps on a 41-step tablet. A quartz glass mask without an exposure pattern was used. After standing at room temperature for 30 minutes, the support was peeled off evaluation laminate A. The entire surface of the photosensitive resin composition layer on evaluation laminate A was spray-developed with a 1% by mass aqueous sodium carbonate solution at 30°C at a spray pressure of 0.2 MPa for 1 minute. After spray development, the yield was 2 J / cm². 2 The photosensitive resin composition layer was cured by irradiating it with ultraviolet light and then heating it at 170°C for 1 hour.

[0226] The evaluation laminate A was immersed in a swelling solution, Sweling Dip Securigand P containing diethylene glycol monobutyl ether, manufactured by Attec Japan, at 60°C for 10 minutes. Next, as a roughening solution, it was immersed in Concentrate Compact P (an aqueous solution of KMnO4: 60 g / L and NaOH: 40 g / L), manufactured by Attec Japan, at 80°C for 10 minutes. Finally, as a neutralizing solution, it was immersed in Reduction Sulfuricine Securigand P, manufactured by Attec Japan, at 40°C for 5 minutes. The laminate after this roughening treatment was designated as Sample A.

[0227] For sample A, the arithmetic mean roughness (Ra) was determined using a non-contact surface roughness meter (WYKO NT3300, manufactured by Bee Instruments) in VSI mode with a 50x lens, resulting in a measurement range of 121 μm × 92 μm. The average of 10 points was then calculated to obtain the measured value, which was evaluated according to the following criteria.

[0228] (Evaluation criteria for arithmetic mean roughness) "〇": Arithmetic mean roughness is less than 200 μm 「△」: Arithmetic mean roughness is 200 μm or more and 400 μm or less 「×」: Arithmetic mean roughness is greater than 400 μm

[0229] <Test Example 5: Evaluation of Peel Strength of Copper Plated Conductor Layer> A sample A similar to that obtained in Test Example 4 was immersed in a solution for electroless plating containing PdCl2 in order to form a circuit on the surface of the insulating layer, and then immersed in an electroless copper plating solution. After annealing by heating at 150 °C for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm. Next, annealing was performed at 180 °C for 60 minutes. The sample thus obtained was designated as sample B.

[0230] A cut was made in the conductor layer of sample B in a portion with a width of 10 mm and a length of 100 mm, one end of this was peeled off and grasped with a gripping tool (manufactured by T.S.E. Co., Ltd., auto-comb type testing machine, AC-50C-SL), and the load (kgf / cm) when peeling 35 mm vertically at a speed of 50 mm / min at room temperature was measured and evaluated according to the following criteria.

[0231] (Evaluation Criteria for Peel Strength) 「〇」: Peel strength is 0.3 kgf / cm or more 「×」: Peel strength is less than 0.3 kgf / cm

[0232] <Test Example 6: Evaluation of Warping> A photosensitive film with a support similar to that obtained in Test Example 1 was laminated on one side of a core material (manufactured by Showa Denko Materials Co., Ltd., "E700GR", size: 16 cm × 12 cm) from which all copper with a thickness of 200 μm in the photosensitive resin composition layer had been etched out using a vacuum laminator (manufactured by Nichco Materials Co., Ltd., VP160), and an evaluation laminated board B in which the core material, the photosensitive resin composition layer, and the support were laminated in this order was produced. The crimping conditions were a vacuum evacuation time of 30 seconds, a crimping temperature of 80 °C, a crimping pressure of 0.7 MPa, and a pressurization time of 30 seconds. After producing the evaluation laminate B, it was left standing at room temperature (25 °C) for 30 minutes or more.

[0233] Ultraviolet exposure was performed on the support of evaluation laminate B using a pattern forming apparatus at an exposure energy that resulted in 8 remaining glossy steps on a 41-step tablet. A quartz glass mask without an exposure pattern was used. After standing at room temperature for 30 minutes, the support was peeled off evaluation laminate B. The entire surface of the photosensitive resin composition layer on evaluation laminate B was spray-developed with a 1% by mass aqueous sodium carbonate solution at 30°C at a spray pressure of 0.2 MPa for 1 minute. After spray development, the yield was 2 J / cm². 2 The photosensitive resin composition layer was cured by ultraviolet irradiation and then heat treatment at 170°C for 1 hour to obtain evaluation core material A.

[0234] Each evaluation core material A was placed on a horizontal platform, one long side was fixed to the platform, and the height of the other long side from the platform (amount of curvature in the short side direction) was measured.

[0235] (Evaluation criteria for warping) "〇": Curvature in the short side direction is less than 10 μm "×": Curvature in the short side direction is 10 μm or more.

[0236] The amount of raw materials used to prepare the resin compositions of each example and comparative example, and the evaluation results of the test examples are summarized in Table 1 below.

[0237] [Table 1]

[0238] From the results shown in Table 1 above, it can be seen that by using a photosensitive resin composition comprising (A) epoxy resin, (B) acid-modified epoxy (meth)acrylate resin, (C) photopolymerization initiator, and (D) inorganic filler, wherein component (D) comprises (D1) an inorganic filler with an average particle size of 20 nm to 90 nm and (D2) an inorganic filler with an average particle size of 100 nm to 500 nm, and component (D1) comprises an inorganic filler surface-treated with an amino-based silane coupling agent, it is possible to obtain a cured product with superior copper plating peel strength and superior resolution. Furthermore, it can be seen that by using such a photosensitive resin composition, it is possible to obtain a cured product with a lower arithmetic mean roughness (Ra) after roughening treatment. Furthermore, it can be seen that by using such a photosensitive resin composition, it is possible to obtain a cured product with a lower mean linear thermal expansion coefficient (CTE).

Claims

1. A resin composition comprising (A) epoxy resin (excluding acid-modified and / or (meth)acrylic-modified epoxy resin and component (F)), (B) acid-modified epoxy (meth)acrylate resin, (C) photopolymerization initiator, (D) inorganic filler, and (F) reactive diluent, Component (D) comprises (D1) an inorganic filler with an average particle size of 20 nm to 90 nm, and (D2) an inorganic filler with an average particle size of 100 nm to 500 nm. Component (D1) contains an inorganic filler surface-treated with an amino-based silane coupling agent. A photosensitive resin composition comprising a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule, wherein component (F) is a (meth)acrylate compound.

2. The photosensitive resin composition according to claim 1, wherein the content of component (D1) is 5% by mass to 30% by mass, when the nonvolatile components in the resin composition are considered to be 100% by mass.

3. The photosensitive resin composition according to claim 1 or 2, wherein the content of component (D2) is 20% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein component (D2) comprises an inorganic filler surface-treated with an amino-based silane coupling agent.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the mass ratio of component (D2) to component (D1) (component (D2) / component (D1)) is 0.5 to 20.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the content of component (D) is 40% by mass or more when the nonvolatile components in the photosensitive resin composition are taken as 100% by mass.

7. (A) The photosensitive resin composition according to any one of claims 1 to 6, wherein component (A) comprises an epoxy resin having a naphthalene skeleton.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein component (B) comprises an acid-modified epoxy (meth)acrylate resin having a naphthalene skeleton.

9. (B) The photosensitive resin composition according to any one of claims 1 to 8, wherein the acid value of component (B) is 1 mg KOH / g or more.

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the weight-average molecular weight of component (B) is 1,000 to 20,000.

11. A photosensitive resin composition according to any one of claims 1 to 10, wherein the mass ratio of component (B) to component (A) (component (B) / component (A)) is 1 to 3.

12. The photosensitive resin composition according to any one of claims 1 to 11, wherein component (C) comprises a photopolymerization initiator selected from α-aminoketone-based photopolymerization initiators and phosphine oxide-based photopolymerization initiators.

13. The photosensitive resin composition according to claim 12, wherein component (C) comprises an α-aminoketone-based photopolymerization initiator having a fluorene skeleton.

14. (E) The photosensitive resin composition according to any one of claims 1 to 13, further comprising a photosensitizer.

15. The photosensitive resin composition according to claim 14, wherein component (E) comprises a photosensitizer selected from thioxanthones and benzophenones.

16. A photosensitive resin composition according to any one of claims 1 to 15, for use in forming solder resist.

17. A photosensitive film with a support, comprising a support and a photosensitive resin composition layer formed on the support using the photosensitive resin composition described in any one of claims 1 to 16.

18. The photosensitive film according to claim 17, wherein the thickness of the photosensitive resin composition layer is in the range of 10 μm to 100 μm.

19. A printed circuit board comprising an insulating layer formed from a cured product of a photosensitive resin composition according to any one of claims 1 to 16.

20. A semiconductor device comprising a printed circuit board as described in claim 19.

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